Poly-acetoacetyl derivatives of polyamines as azo components in diazotype photoprinting material



Patented Sept. 7, I954 POLY-ACETOACETYL DEREVATIVES 0F POLYAMINES AS AZOCOMPONENTS IN DIAZOTYPE PHOTOPRINTING MA- TERIAL William vonGlahn,;Loudonville, and Lester N. Stanley, Delmar, N; Y., assignors toGeneral Aniline & Film Corporation, New York, N. 'Y., a corporation ofDelaware No Drawing. Application December 20, 1950,

Serial N 0. 201,872

6 Claims.

This invention relates to a diazotype process and more particularly tothe use of certain azo components in the light-sensitive layer of adiazotype reproduction medium or in a developing solution for theexposed diazotype image. This application is a continuation-in-part ofour copending application Serial No. 704,302, filed October 18, 1946,now Patent No. 2,537,106.

In the reproduction of mechanical drawings, printed material, pictures,or other originals to be copied, it is of particular advantage in manycases to make first an intermediate print or transition print on atransparent diazotypecopying material by exposing the transparentsensitized diazotype material to actinic rays such as ultraviolet lightby either the printing through or reflex process and then developing thediazotype material. The development of such diazotype prints may becarried out by any of the developing methods known to the art fordevelopment of exposed diazotype materials. Thus, where a two-componentsystem is employed containing the axe component in the light-sensitivelayer with the diazo compound, development is effected by passing theexposed diazotype through ammonia vapors, and

where a one-component system is employed which contains the diazocompound. as the only dye component in the light-sensitive layer, theimage is developed by treating the exposed diazotype with an alkalinesolution containing the azo component by a dipping or fog sprayingmethod. The image thus produced on the transparent intermediate ortransition diazotype print can be used for reproduction of furtherdiazotype prints of high contrast. for the reproduction of the image onany suitable photopr-inting material such as silver halide photographicpaper and Van Dyke prints and blueprints.

This method of producing transition diazotype prints is particularlyuseful when it is desired to make a number of reproductions from a frailor valuable original which would be adversely affected if not destroyedin the repeated exposures necessary to make the desired number ofcopies. 4

It is essential in the so-called reflex process where the diazotype copymaterial is superimposed on the opaque original to be copied and thelight for exposure of the diazotype material-passes through it and isreflected by the surface of the original.

The efliciency of the process involving the production of a transitionor intermediate print depends upon the opacity of the azo dye imageproduced upon such intermediate or transition print to ultraviolet'lightand upon the transparency of If desired, they can also be used thebackground to such light. It depends also upon the visual density of theimage produced on the intermediate or transition print, since images ofpoor visual density such as light yellows on a white ,or transparentbackground, though they may have the desired degree of opacity toultraviolet light, nevertheless have the disadvantage of renderingdifiicult the detection of flaws in the intermediate image. With suchprints, it is necessary to make a contrast print of good visual densityfrom the intermediate before such flaws can be detected, therebyintroducing an addi tional and unnecessary step.

Print of a' deep color having good visual density can be obtained from.diazotypes using azo components common .to the art for the productionof ordinary diazotypes such as phloroglucin, 2,3- dihydroxynaphthaleneand B-naphthol-ZtLG-disulionic acid. However, despite the good visualdensity of the .color reproducing the image, its actinic opacity orphotographic density is not sufilcient to reproduce the imagesatisfactorily in subsequent copies. The azo ,dye component used for theproduction of transition print images must be such as to produce uponcoupling with the diazo compound employed a color which willsufficiently absorb the ultraviolet light incident upon it duringexposure to prevent light decomposition of the diazo compound in theareas to be reproduced from the transition copies. Colors of good visualdensity do not necessarily have this property. It is well known, forinstance, that blues such as are produced from azo .components likephloroglucin are very poor in their ultraviolet absorptioncharacteristics.

Azo components such as resorcinol have heretofore been employed in theproduction of diazotype prints in order to obtain color images havingthe necessary light absorption characteristics for transition printing.Resorcinol will reproduce the image on the transition print in a sepiaor orange-brown color which has good opacity to ultraviolet light andhas sufficient depth of color or visual density to assure detection ofprinting flaws and the like in the developed intermediate print. Otherazo components have been suggested which will produce images of goodopacity or covering power when used in combination with polyhydroxy azocomponents such as phloroglucinol and resorcinol. These azo componentsare aoetoacetyl derivatives of mono-amines and are disclosed in PatentNo. 1,989,065. However, although these acetoacetyl derivatives ofmonoamines may produce satisfactory results as shaders for other colorswhich may lack the necessary covering power, particularly in copyinghalf tones or too light lines, they do not produce satisfactory imageswhen used as self colors, that is, when the acetoacetyl derivatives ofmonoamines, such as the cyclohexyl acetoacetic acid amide and the likedisclosed in Patent No. 1,989,065, are used as the only azo componentsfor the development of a diazotype print, the image produced does nothave a satisfactory shade or tone value.

It has now been found that the polyacetoacetyl derivatives of aliphaticaromatic, or heterocyclic polyamines are especially effective as azocomponents for diazotype reproductions. This class of azo components canbe used satisfactorily either alone in the production of self shades orin combination with other azo components for shading purposes. In eithercase the resulting images have excellent opacity characteristics. Theopacity to ultraviolet light and covering power of the self shadesmarkedly surpass those properties of colors produced from themonoacetoacetyl derivatives, and when used for shading purposes incombination with such azo components as phlaroglucinol,2,3-dihydroxynaphthalene, or 2,3- dihydroxynaphthalene sulfonic acid,excellent neutral blacks having good opacity to ultraviolet light areobtained. In general, these polyacetoacetyl derivatives are preparedfrom the corresponding polyamine by reaction with acetoacetic esters orwith diketenes. The acetoacetic esters or diketent condenses with theamino groups of the polyamine, thus forming amide linkages. The aminemay be any aliphatic, aromatic, or heterocyclic polyamine wherein thealiphatic chain or aromatic or heterocyclic nuclei may be substituted byany of the uuual substituents such as alkyl, halogen alkoxy, carboxy,sulfo, hydroxy, or other groups which do not discolor the paper orimpair the solubility characteristics of the azo component. (Forexample, nitro groups discolor the paper.) This class of azo componentsmay be represented by the following general formula: R(COCH2COCH3)nwherein R is an aromatic, or heterocyclic polyamino radical and n is awhole number greater than one and each acetoacetyl group is attached toan amino nitrogen atom of R. Examples of polyacetoacetyl derivatives ofthis class are:

(1) 2,4-diacetoacetamino-benzene sulfonic acid SOzH NHCO CHzC CH:

NHCOCHaC O CH:

NHO OCHaGO OH:

(3) Bis-acetoacet-o-or m-dianisidide CHaCOCHzCONH NHCOCHzCOGHa (4)Diacetoacetyl-piperazine CH2-CH2 N o o 0 mo 0 c H;

CHr-C 2 (5) N,N-diacetoacetyl-4-amino piperidine CHz-CH:

NC 0 CHzC 0 CH:

C Hr C i (6) Diacetoacetyl-melamine CHaC O CHzC ON CHaC 0 CHzC ONHHCCHaCOOHzCOHN? fi-NHCOCHaCOCH;

('7) Diacetoacetyl-benzidine ornooomooHN-OONnooomoooH.

(8) l ,4-diacetoacetamino-naphthalene CHaCOCH2COHN NHCOCHzCOCHs In thepreparation of diazotype materials intended for use as intermediate ortransition print media in accordance with this invention, a suitabletransparent base such as transparentized paper, cellulose acetate film,or other transparent material is coated by means known to the art with alight-sensitive composition containing suitable diazo compounds. Whereit is desired to make a two-component diazotype layer on the support orbase material for development by the dry developing method, the azocomponent is also incorporated into the coating composition. Whereone-component diazotype layers are desired the azo component is added toan alkaline developing solution and after exposure of the diazotype theexposed image is developed by contacting with the alkaline developingsolution by means known to the art. In the preparation of coatingcompositions for two-component diazotype layers, the coating solutionmay also contain such other materials as are ordinarily used in thepreparation of diazotype two-component light-sensitive coatingcompositions. These include stabilizing materials such as citric acid,phosphoric acid, and thiourea; swelling agents for cellulose acetate andother cellulosic ester bases such as isopropanol; and shade intensifyingagents such as nickel sulfate. In the preparation of light-sensitivelayers on paper :for the production of neutral black images or dark toneimages which may or may not be intended for reproduction of furthercopies, it is preferable to employ a two-component coating compositionwhich will contain one or more dark tone producing azo components,preferably such as will produce blue shades with the diazo compoundsemployed in combination with the polyacetoacetyl amino azo components ofthis invention. The diazo compound or compounds and other adjuvants areadded to the coating composition and the paper used as a carrier for thelight-sensitive layer is coated in the same manner as thetransparentized paper or cellulosic film base material in the case ofthe transition print media. As diazo compounds any suitablelight-sensitive diazo compound which will couple with the azo componentsto reproduce a colored image may be employed.

acsasca We prefer, however, to use diazo compounds derived fromp-diamines of the benzene series, par ticularly when two-componentcoating composttions are employed. As is well known in the art, thisclass of diazo compounds is especially suit able for the 1." oduction oftwo-component diazo" type photo-sensitized papers. Other diazo compoundshave been found suitable for use such as diazo anhydrides ofaminohydroxynaphthalene compounds are less extensively employed. Thep-diamines most generally used for production of the diazo compounds arethose wherein one of the amino groups is unsubstituted fordiazotiz-ation and the other is substituted by such groups a" allzyl,allzoxy-alkyl, aryl, aralkyl, alkylol, cycloaliphatic and heterocyclicgroups. Examples of these amines from which the diazo compounds arederived include N-hydroxythyl-N-methylamino p aininobenzene; p-aminodiphenylamine; l-mono-methyla:nino-2.(or 3) -methyl-- aminobenzene;l"l-hydroxyethyl-N-ethylamino- 3-methyl aminobenzene; ,1-diethylamino-3-nohenzene; s-amino-l-benzoylamip-amino-N-diethylanithoxy'cenzene;

p-amino-N-ethyl -N benzylaniline; l-ethy -azzninobenzene;l-N-hydroxyethyl-N-ethyla ol-arninobenzene; p-phenylene diamine; amino-l l,N- dihydroxyethylaniline;

aminooenzene:

p-- l -ethoxy henyl) amino-2,5-diethoxyaniline;

l-N-ethylarr -2methyl4-arninobenzene; l-diinethylam.o-3-methoxy-4l-aminobenzene; N,N- -paminobenzene; l-dimethylamihylaminobenzene; p-aminophenyl morpholine and 2-amino-l-naphthol-5-sulfonicacid. The diazo derivatives of these amines are used in the form oftheir stabilized salts, such as the 211212, CdCla or 811012 doublesalts, fluoroborates, aryl or alkyl sulfonates, and acid sulfates of thediazoniuin chloride.

fol? specific examples will serve to illustrate in 1 r the invention, itbeing understood, hortcwr, that they are not intended to limit itsscope. Unless otherwise stated, the parts are by weight.

Example 1 Transparentized paper is coated'with a coating solutioncontaining the following ingredients per 100 co. in a 5% aqueoussolution of alcohol:

5.0 g. 2,4-diacetoacetarnino-benzene sulfonic acid 3.8 g. N-methyl,N-hydroxyethylamino-p-benzene diazonium chloride-ZnCh double salt 4.0 g.thiourea 8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zinc chlorideOrdinary paper stock for diazotropes is coated l-l l,l ldihydroxyethylamino -3-chloro-4- with a coating solution containing thefollowing ingredients per cc. .of a 3% aqueous solution of isopropanol:

1.0 g. 2,4-diacetoacetamino-toluene 3.0 g.2,3-dihydroxynaphthalene-6-sulionic acid 0.12 g.2,8-dihydroxynaphthalene 3.0 g. N;N-diethylamino-p-benzene .diazoniumchloride-211012 double salt 5.0 .g. 'ZnClz 10.0 g. citric acid 2.0 g.phosphoric acid 5.0 g. thiourea The coated paper is first dried in theusual manner and is then exposed under a pattern and gleveloped bycontacting with ammonia fumes. The prints thus developed are a neutralblack shade having ood gradation and showing little tendenc y for colorshift upon standing. These prints also have good opacity to ultravioletlight and good light-fastness and wash-fastness properties.

Upon substituting the following mixtures of oz! components for the threeazo components in the formula of this example, diazotype prints havmgsimilar characteristics and properties are obtained 1.0 g.bis-acetoacet-o-dianisididc 2.8 g. 2,3adihydroxynaphthalene-6esulionioacid 0.1 g. 2,3-dihydroxynaphthalene The coating, formula and procedureare otherwise the same as in thi sexample. The compositions of thisexample illustrate the utility of the polyacetoacetyl polyamines of thisinvention for shading to neutral blacks when they are used in mixturewith azo components which normally develop to a blue shade. Other azocomponents which will develop blue shades, such as phloroglucinol, maybe substituted for or combined with the 2,3-dihydroxynaphthalenecouplers of this example with similar results and azo components whichwill produce tones other than blue may also be used in combination withthe polyacetoacetyl polyamines to produce modified tones which will havegood covering power and opacity 0t ultraviolet light.

Example 3 Transparentized paper is coated with a coating solutioncontaining the following ingredients per 100 co. in a 5% aqueoussolution of alcohol:

5.0 g. diacetoacetyl piperazine 3.5 g. N,N-diethylamino-p-benzenediazonium chloride-ZnClz double salt 4.0 g. thiourea 8.0 g. citric acid2.0 g. phosphoric acid 5.0 g. zinc chloride The coated transparency isfirst dried in the usual manner andis then exposed to light under apattern and developed by contacting with ammonia fumes. The image of thepattern is developed in a sepia shade which possesses excellent opacityto ultraviolet light. It is, therefore, well suited for furtherreproduction work as a transition print. Its light-fastness andwash-fastness properties are similar to the prints obtained inaccordance with Example 1.

Example 4 Transparentized paper is coated with a coating solutioncontaining the following ingredients per 100 cc. in a 5% aqueoussolution of alcohol:

5.2 g. diacetoacetyl-4-amino piperidine 3.6 g.1-N-ethylamino-2-methyl-4-benzene diazonium chloride-ZnClz double salt4.0 g. thiourea 8.0 g. citric acid 2.0 g. phosphoric acid 5.0 g. zincchloride The coated transparency is first dried in the usual manner andis then exposed to light under a pattern and developed by contactingwith ammonia fumes. The image of the pattern is reproduced in a sepiashade having excellent opacity to ultraviolet light. The light-fastnessand wash-fastness properties of this print are also good and it isparticularly suited for use as a transition print in the reproduction offurther copies.

We claim:

1. The process of producing azo dye images in a light sensitivediazotype material comprising a base carrying a light sensitivediazonium compound which comprises exposing said light sensitivematerial through a pattern to actinic light to destroy the diazoniumcompound which is struck by light and treating said material with analkali in the presence of an azo coupling component of a polyacetylderivative selected from the class consisting of aryl polyamines of thebenzene and naphthalene series and B-membered nitrogenous heterocyclicpolyamines in which the acetoacetyl groups are attached to aminonitrogen atoms of the polyamines to effect coupling of said azo couplingcomponent with residual diazonium compound.

2. The process as defined in claim 1 wherein the azo coupling componentis present in the light sensitive diazotype material. 1

3. A light-sensitive ,material for the production of diazotype printscomprising a flat carrier base having coated thereon a light-sensitivediazo compound and as azo component the compound 2,4 diacetoacetaminobenzene sulfonic acid, having the structural formula:

lOaH NHCOCHICOCHS NHCOCHaCOOHs 4. A light-sensitive material for theproduction of diazotype prints comprising a fiat carrier base havingcoated thereon a light-sensitive diazo compound and as azo component thecompound diacetoacetyl piperazine having the str tural formula:

5. A light-sensitive material for the production of diazotype printscomprising a fiat carrier base having coated thereon a light-sensitivediazo compound, and as an azo component the compoundbis-acetoacet-o-dianisidide having the structural formula moo c1120 0OHNOONHC o CHaC 0 on;

(gcHa $CH:

and another azo component.

6. A light-sensitive material for the production of diazotype printscomprising a flat carrier base having coated thereon a light-sensitivediazo compound, and as an azo component the compound2,4diacetoacetamino-toluene having the formula H30 0 CHzC O C-NNHOOCHzCOCHa NBC 0 cmc 0 CH3 and another azo component.

References Cited in the file of this patent UNITED STATES PATENTS

1. THE PROCESS OF PRODUCING AZO DYE IMAGES IN A LIGHT SENSITIVEDIAZOTYPE MATERIAL COMPRISING A BASE CARRYING A LIGHT SENSITIVEDIAZONIUM COMPOUND WHICH COMPRISING EXPOSING SAID LIGHT SENSITIVEMATERIAL THROUGH A PATTERN TO ACTINIC IS STRUCK BY LIGHT AND TREATINGSAID MATERIAL WITH AN ALKALI IN THE PRESENCE OF AN AZO COUPLINGCOMPONENT OF A POLYACETYL DERIVATIVE SELECTED FROM THE CLASS CONSISTINGOF ARYL POLYAMINES OF THE BENZENE AND NAPHTHALENE SERIES AND 6-MEMBEREDNITROGENOUS HETEROCYCLIC POLYAMINES IN WHICH THE ACETOACETYL GROUPS AREATTACHED TO AMINO NITROGEN ATOMS OF THE POLYAMINES TO EFFECT COUPLING OFSAID AZO COUPLING COMPONENT WITH RESIDUAL DIAZONIUM COMPOUND.